具有生物活性的金属配合物的研究 III: 3-6(二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物的合成, 性质及抗肿瘤活性

合成了十五种新的3,6-二(二甲氨基)-二苯并碘六环稀土二柠檬酸配合物, 其化学式为: [C17H20N2I]3[RE(C6H5O7)2].xH2O(RE=La-Nd, x=5; Sm-Tb, x=4; Dy-Lu, Y,x=3). 利用X射线粉末衍射、热重-差热, 红外光谱、紫外光谱、摩尔电导等对这些配合物进行了表征. 试验表明, 镧配合物对L7712癌细胞DNA合成的抑制率(97.3%)明显高于其前体(C17H20N2I^+.HCOO^-, 72.5%; Na3[La(C6H5O7)2], -16.5%.     

双-(二烷硫基四硫富瓦烯二硫)金属配合物的合成及性质研究

合成了三种未见文献报道的双-(二烷硫基四硫富瓦烯二硫)金属配合物和三种新的四硫富瓦烯(TTF)桥联的双金属配合物,测定了它们的导电率,讨论了含Ni配合物的电导率优于含Cu,Hg配合物的原因。     

新型二茂稀土烃硫基配合物的合成与表征

本文用三茂基稀土[(C~5H~5)~3Ln(Ln=Ho(1)，Yb(2)，La(3)，Y(4)]与等摩尔的2-巯基嘧啶(HSC:NCH:CHCH:N·)在四氢呋喃溶剂中于室温下反应，合成了四个对空气敏感的二茂稀土嘧啶巯基配合物。产物经元素分析、红外光谱及质谱鉴定确定其组成为：(C~5H~5)~2LnSC:NCH:CHCH:N·THF[Ln=Ho(1)，Yb(2)，La(3)，Y(4)]。     

环戊二烯基轻稀土二氯化物邻菲罗啉配合物的合成

用LnCl~3邻菲绕啉和C~5H~5Na在四氢呋喃中的反应合成了四个1,10-二氮杂菲配位的含四氢呋喃的轻稀土环戊二烯二氯化物。用元素分析、红外光谱、电子能谱、差热分析等方法鉴定了这四个新化合物。     

二甲氧基嘧啶胺与金属配合物的恒容燃烧热测定

在无水乙醇中，使钴、铜、锌、锰的盐与二甲氧基嘧啶胺(AMP)反应，回流数 小时后，浓缩、冷却，抽滤，制得了6种二甲氧基嘧啶胺与钴、铜、锌、锰的固态 配合物．用化学分析和元素分析确定了它们的组成，分别为Co(AMP)_2Cl_2(1)， Cu(AMP)_2Cl_2(2)，Cu(AMP)_2(NO_3)_2(3)，Zn(AMP)_2Cl_2(4)，Mn(AMP) _2Cl_2(5)和zn(AMP)s04(6)；用IR，～1H NMR研究了他们的成键情况；用精密转动 弹热量计测定了配体及配合物的恒容燃烧热△_cU，计算了它们的标准摩尔燃烧焓 △_cH_m～θ和标准摩尔生成焓△fH_m～θ．     

β—二酮型钴和镍配合物液晶的合成与表征

合成了β-二酮型钴和镍配合物。通过元素分析、IR、NMR、热台偏光显微镜、DSC和WAXS等观测,表明两个配合物皆为热致性向列型液晶。     

二嗜性配合物四（α—噻吩甲酰三氟丙酮）含铕酸十六烷基吡啶的…

含成了具有极强荧光和良好单色性的标题配全物，用红外，紫外，热分析及Ｘ射线粉末衍射等进行了表征。研究了成膜性能，为制备高密度、超薄光学存贮材料提供了实验证据。     

碱土金属邻苯二甲酸盐的振动光谱

测定了CaPHT·H_2O和两种CaPHT的晶体结构,其空间群分别属于P2_1/c(C_(2h)~5,Z=4),P2_1/m(C_(2h)~2,Z=8)和 P2/m(C_(2h)~1,Z=6).研究了 CaPHT·H_2O、CaPHT(A)、CaPHT(B)、MgPHT、SrPHT 和 BaPHT 的 IR 及 CaPHT·H_2O 的拉曼光谱,讨论了固体样品中 PHT 与碱土金属离子的配位结构及其对光谱的影响.     

Quinoline-based tetradendate nitrogen ligands stabilize the bis(micro-oxo) dinuclear manganese(iii,iii) core

Quinoline-based, tetradentate nitrogen ligands, N,N'-bis(2-quinolylmethyl)-N,N'-dialkyl-1,2-ethanediamine (alkyl = methyl, bqdmen; ethyl, bqdeen; isopropyl, bqdpen), have been investigated as the supporting ligands for the formation of bis(micro-oxo) dinuclear manganese complexes. Bis(micro-oxo)Mn(2)(iii,iii) complexes and were obtained for bqdmen and bqdeen, respectively, as evidenced by X-ray crystallography, whereas bqdpen did not afford any manganese complexes due to its steric bulk. Complexes and exhibit highly positive Mn(2)(iii,iii)/Mn(2)(iii,iv) and Mn(2)(iii,iv)/Mn(2)(iv,iv) redox couples relative to the corresponding pyridine-ligated (micro-O)(2)Mn(2)(iii,iii) complexes.     

Neodymium(iii) and dysprosium(iii) naphthalene hydride complexes

Reactions of neodymium and dysprosium diiodide hydrides LnI₂H with lithium naphthalenide in THF furnished heterobimetallic naphthalene hydride clusters (C₁₀H₈)₃Ln₅Li₅H₁₄ (Ln = Nd, Dy). Treatment of the latter with hexamethyldisilazane in THF leads to the removal of lithium in the form of LiN(SiMe₃)₂ and the formation of compounds of the composition (C₁₀H₈)₃Ln₅H₉ (Ln = Nd, Dy). All the clusters obtained were isolated as black pyrophoric powders insoluble in THF and other organic solvents. Reactions of (C₁₀H₈)₃Nd₅Li₅H₁₄ and (C₁₀H₈)₃Nd₅H₉ with cyclopentadiene lead to Cp₃Nd(THF).     

Complexes of gold(iii) and titanium(iii) with 8-hydroxyquinoline

The preparation of an 8-hydroxyquinoline complex of trivalent gold by the action of oxine upon gold chloride and “monopyridine gold chloride” is described. The absorption spectrum of the complex, which approximated to the composition AuCl₂C₉H₆ON was plotted in the U.V. and visible regions of the spectrum.A partial separation between tri- and tetravalent titanium was obtained using paper chromatography. Absorption curves were obtained for oxine complexes of Ti(III) and Ti(IV) in the visible region of the spectrum.     

The structure of di-μ-pentafluorobenzoatobis[bis(pentafluorophenyl)(triphenylphosphine oxide)thallium(iii)]

An X-ray crystallographic study has shown that the complex (C₆H₅)₂TlO₂CC₆F₅(OPPh₃) has a dimeric structure with unsymmetrical pentafluorobenzoate bridging (TlO 2.531 and 2.789 Å) but an exact crystallographic centre of symmetry. The pentafluorobenzoate groups are also unsymmetrically chelated to thallium (TlO 2.389 and 2.531 Å.), which overall has irregular six coordination.     

Nanoparticles based on gadolinium(iii) and europium(iii) complexes for biovisualization

Complexes Ln(TTA)₃ and [Ln(TTA)₃·1] (Ln = Eu, Gd; ТТА is thenoyltrifluoroacetyl-acetonate; 1 is 2-(5-chlorophenylene-2-hydroxy)-2-phenylethylene-bis(2-methoxy)phosphine oxide) in individual form, and as a part of a core of the polyelectrolyte stabilized colloids have been studied by Mössbauer spectroscopy and X-ray powder diffraction. The photophysical and colloidal characteristics of the solutions of polyelectrolyte nanoparticles were studied in water, artificial cerebrospinal fluid solution, solution of bovine serum albumin, and human blood serum. A stability of a luminescent response of the nanoparticles in solutions of bovine serum albumin and human blood serum at 37 °С for 2 hours has been revealed. This is a prerequisite for the potential application of studied nanoparticles for biovisualization.

     

Unusual nitro-coordination of europium(iii) and terbium(iii) with pyridinyl ligands

A new ligand family based on picoline, bipyridine and terpyridine containing a nitro moiety has been synthesized and its coordination and sensitization ability for lanthanide ions has been studied. Three new complexes were characterized by X-ray single crystal diffraction and all three show uncommon coordination of the nitro moiety to the lanthanide ion. , a terpyridine-nitro derivative with Tb(NO(3))(3), crystallizes in the orthorhombic space group Pbca with a = 15.125(3), b = 13.776(3), c = 18.716(4) ?, and V = 3899.8(13) ?(3) and is isostructural with its Eu(iii) analog () with cell parameters a = 15.1341(4), b = 13.7070(4), c = 18.8277(5) ?. , a tripodal amine with a nitro-derivatized pyridine with Eu(CF(3)SO(3))(3), crystallizes in the triclinic space group P1[combining macron] with a = 11.067(2), b = 11.633(2), c = 12.772(3) ?, α = 110.94(3), β = 97.49(3), γ = 91.42(3)° and V = 1518.1(5) ?(3). Finally, ligand , a bipyridine-nitro derivative, crystallizes in the orthorhombic space group P2(1)/n with a = 3.7128(3), b = 11.7806(8), c = 19.9856(14) ?, β = 92.925(2)° and V = 873.01(11) ?(3). All four ligands show sensitization of Eu(iii) and Tb(iii) luminescence.     

Novel redox active rhodium(iii) complex with bis(arylimino)acenaphthene ligand: synthesis,structure and electrochemical studies

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